Preparation of organic mercuric nitrate



Patented Jan. 2, 1945 a he 2,366,683

x NITED STATES PAT T L OFFICE A i PREPARATION F ORGANIC MERCURIC v j nNITRATE a Harland H. Young, Chicago, IlL, assignor to Industrial PatentsCorporation, Chicago, 111., a

corporation o f Delaware Application February 19, 1942; SerialNo.431,495j No Drawing.

6 Claims. (01.260 43) This inventionrelates to the synthesis of organicmercuric nitrates.

This application is-a continuation in partof my co-pending applicationentitled Preparation of organic mercuric nitrate, filed October 30,1939. a

One of the objects of the invention is to provide a novel and lessexpensive method for the preparation of such compounds than isnowemployed. 1 I

Other objects of the invention will beapparent from the description andclaims which follow.

Various organic mercuric nitrates are of technical importance, the mostimportant ofthes e compounds commercially being phenyl mercuric nitratewhich is widely used in certain quarters V for its bactericidal anddisinfectant properties.

, By way of illustration but not by way of limitation the presentinvention will be described as applied to the prepaartion of phenylmercuric nitrate, which is an aryl mercuric nitrate.

Heretofore known synthesis for phenyl men curic nitrate starts with themercuration of benzene by means of mercuric acetate. The result- -antphenyl mercuric acetate is converted to the phenyl mercuric chloride andthence to the nitrate. Phenyl mercuric chloride is obtained from theacetate by reacting the acetate with calcium Serial No. corpse,

phenyl has been reacted with oxides of nitrogen and mercuric nitratealone, butthe yields are not satisfactory. l

A common method for converting phenyl mercuric chloride to phenylmercuric nitrate is by means of alcoholic solutions of silver nitratewhich is an expensive reagent and entails subsequent recovery of thesilver, resulting in a high cost end product.

It has also been proposed to prepare phenyl mercuric nitrate byvigorously shaking a solution of diphenyl mercury in chloroform with anaqueous solution of mercuric nitrate. This method is not entirelysatisfactory and the maximum yield which is obtainable is about '75 percent.

In preparing phenyl mercuric nitrate by the present invention, benzeneis mercurated with mercuric acetate, resulting in phenyl mercuricacetate. The phenyl mercuric acetate is reduced to mercury diphenyl,which is then quantitatively converted to phenyIJmercuric nitrate by asolution of mercuric nitrate in acetone, water, and nitric acid. i

In carryingout the present invention, the

proper ratio of water, nitric acid, and acetone is, of course,maintained. It is well known that mercuric nitrateis insolubleinacetone, but is: very soluble in water. In aqueous solutions, itdecomposes to a basic nitrate'unless nitric acid is present. Mercurydiphenyl is soluble in acetone, but is insoluble in water. These factshave heretofore prevented thepreparation of phenylfmercuric nitratebythe direct reaction of nitrate and mercury diphenyl y The manner inwhich the present invention overcomes this difliculty will be clear fromthe following example:

mercuric Example 1"mol.. or mercury diphenyl was dissolved in acetone toform a per centsaturated solution. A solution was then prepared bydissolving 1 mol. of mercuric .nitrate in a minimum. quantity, of watercontaining ,enough nitric acid to. prevent the formation of abasicmercuric nitrataand to dissolve anybasic nitrate-which may havebeenprecipitated by the solution. The concentrated solution-of mercuricnitrate in dilute nitric acid was then diluted'with acetone until itsvolume was substantially equal to that of the mercury diphenyl solution.The two solutions were then mixed by stirring and warmed to 45 degrees0., whereupon phenyl mercuric nitrate began to precipitate in a shorttime, the reaction being substantially complete in thirty minutes andcomplete in one hour.- After completion of the action, the material wascooledand the phenyl mercuric nitrate separated by filtration, somelast,

traces being obtained by evaporating the mother liquor.

I have found inpractice that from 0.1 per cent to 5 per cent nitric acidis sufficient to prevent the formation of a basic mercuric nitrate upondissolving mercuric nitrate in Water. I have also found that ifturbidity occurs in the mercuric ni poses of the present invention arethe phenyl, -;-naphthyl and. phenanthryl.groups. The naph- 'methylphenyl-;. pentamethylphenyl;i and; \orthm, tmetae, and para-biphenylvvtory for the purposes of the -present. invention degrees C. and 50degrees C. It will be understood, of course, that the materials might berefluxed with equally satisfactory results.

4 It will be readily understood that the present invention in itsbroader aspects is not limited to'the preparation of phenyl mercuricnitrate, but includes thegpreparation oi compounds hay-- ing the generalformula RHgNOr-where R is an aryl, substituted aryl, alkyl, substitutedalkyl, or

the radical from the R position of any mercury" derivative having thegeneral formula .RzHgJ which is formed by the reduction of any mercuricacetate having the general formula I RHgOOCCFh; Examples of the variousradicals or groups which are satisfactory for the punposes lofyithegpresent invention are as follows: Aryl groups which are satisfactory forthe pur- :thyh groups; .or :radicaltmay be of the: two isomers,.and-thephenanth-ryI-iriadical may heiany lot the five .isomerseoflithis ;ratlica:1..

=The ibllowi-ngsubstituted zaryl c gmnps orrad-i cals are satisfactoryfor the purposes ot' yention: tolyl; or-thometalandnpara-xylyl; orsynonymously, dimeth ylphenyl; .chIorophen-yl, tor exam-pie,parachiorophenyl \trini'tnophenyl; tri- Alkyl groups which. aresatisfactory .for the preparation {of organic lmetcuaric nitrates .inaccordance with the present invention include the .following groups orradicals; :methyL, ethyl; n

propyl, isopropyl, n-butyL isobutyls-isec-butyl, tert-butyl, isopenty-ltert-pentyl-,,. iri-heptyl. noctyl andsec-octylt y l Substituted alkylgroups which are satisfacare benzyl, phenacyl, and B-carboxyl ethyl anddicarbethoxy methyl; l it is apparent froml the foregoing descriptionthat the-method 0f 'thisiinventfon is not "limited 1 to "thepreparation. of ph'enyI mercuric :nitratze 45 nor is" it limited "to the"preparation of organic mercuricnitrateszofthe specific groupsset'iorth;It is obvious that various modifications of the invention. may he made.without departing; from the spirit and scope: fliereof.

mercuricnitra'te.

I claim:

1. The method of preparing phenyl mercuric nitrate which comprisesconverting mercury diphenyl to phenyl mercuric nitrate by reactingmercury diphenyl with mercuric nitrate in a solution comprising acetone,water, and nitric acid "in sufiicient amount t'ot prevent precipitationof basicmer'curionitrate, the proportion of acetone being sufiicient todissolve the mercury diphenyl.

2. Th method of preparing phenyl mercuric nitrate which comprisesreacting a solution of mercury diphenyl inacetone with a solution ofmercuric nitrate in water and nitric acid in sufe I "ficientamount toprevent precipitation of basic 3.. The-methodof preparing phenylmercuric nitrate which comprises reacting a solution of mercury diphenylin acetone with a solution of mercuric'nitrate in water and nitric acidin sufmercuric nitrate by mixingthetwonolutionscnd mercury diphenylqinacetone with a solutionnf from $0 degrees to mercuric nitrate .inwaterand nitric acidin sut ficient amount to prevent precipitation of: basicmercuric nitrate by mixing thetwo-isolutionsin the proportion ofonemole; of mercury diphenyl to zone- .mole of. mercuric nitrate, andheating until phenyl :mercunio nitrateis precipitated 6. The method of,preparing phenmmercuric nitrate which comprises reacting a. solution" ofmercury .dip'hen-yl lacetune a solution of mercuric nitrate in water andnitric ac-ideinisufiificient .amount. to prevent precipitation. rotbasic mercuric tnitrateby mixing the two solutionsvin the proportion ofone mole of mercury diphenyl to. one mole {if mercuric nitrate, andheating .540 degreesC.

HARE-AND H. YOUNG.

